CN100344037C - Metal element with chromate membrane for plug use and preparation process thereof - Google Patents
Metal element with chromate membrane for plug use and preparation process thereof Download PDFInfo
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- CN100344037C CN100344037C CNB021504563A CN02150456A CN100344037C CN 100344037 C CN100344037 C CN 100344037C CN B021504563 A CNB021504563 A CN B021504563A CN 02150456 A CN02150456 A CN 02150456A CN 100344037 C CN100344037 C CN 100344037C
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- chromate film
- plug
- hardware
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- metal shell
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/84—Dyeing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23Q—IGNITION; EXTINGUISHING-DEVICES
- F23Q7/00—Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
- F23Q7/001—Glowing plugs for internal-combustion engines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T13/00—Sparking plugs
- H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T13/00—Sparking plugs
- H01T13/20—Sparking plugs characterised by features of the electrodes or insulation
- H01T13/32—Sparking plugs characterised by features of the electrodes or insulation characterised by features of the earthed electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T21/00—Apparatus or processes specially adapted for the manufacture or maintenance of spark gaps or sparking plugs
- H01T21/02—Apparatus or processes specially adapted for the manufacture or maintenance of spark gaps or sparking plugs of sparking plugs
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23Q—IGNITION; EXTINGUISHING-DEVICES
- F23Q7/00—Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
- F23Q7/001—Glowing plugs for internal-combustion engines
- F23Q2007/004—Manufacturing or assembling methods
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Spark Plugs (AREA)
Abstract
A chromate film-containing plug metal component which is a metal component for a spark plug or a glow plug, wherein: the metal component has a surface, at least part of the surface being coated with a chromate film comprising at least 95% by weight of trivalent chrome based on 100% by weight of a total chrome content in the chromate film; and the chromate film comprises dye particles.
Description
Technical field
The present invention relates to a kind of plug hardware with chromate film, it has one and is formed on the lip-deep chromate film of its at least a portion, and relates to the preparation method of this hardware.
Background technology
In order to prevent the hardware corrosion, plated film is carried out on the surface of hardware usually, and further applies with chromate film.A kind of chromate film of colour is as a kind of extensive fields that is used in this kind chromate film, and this is because the corrosion resistance excellent of this colored chromate film.But from the position of environmental protection, the same chromate film with excellent corrosion resistance of many and colored chromate film is not used, and this is because they are tending towards containing Cr VI.Hereinafter, main chromyl chromate film also is known as " hexavalent chromate film ".
In order to address this problem, the inventor has developed a kind of Cr VI that is substantially free of still with the chromate film of trivalent chromium as most of chromium component.Hereinafter, this kind chromate film also is known as " trivalent chromate film ".The inventor has successfully kept good corrosion resistance by making the chromate film thickening.As mentioned above, because Cr VI is disabled in the world basically, replacing the hexavalent chromate film with the trivalent chromate film is a progress.
On the other hand, the trivalent chromate film is coated in plug (plug) usually with on the hardware, as spark plug or glow plug.Be higher than the anti-corrosion main topic of discussion that becomes under the temperature of normal temperature, because this kind plug uses in the back that links to each other with internal combustion engine.Even the inventor has developed a kind of good corrosion proof trivalent chromate film that at high temperature also has, and prepared spark plug or the glow plug that this kind chromate film is arranged on it, as disclosed among JP-A-2000-252042 (term used herein " JP-A " refers to " not examining disclosed Japanese patent application "), the JP-A-2000-249340 etc.
Summary of the invention
But,, comprise that the hexavalent chromate film of colored chromate film can show various tones when Cr VI is contained in the film and the thickness of film when changing dispersedly.Yet, can not make the trivalent chromate film show the various tones identical with the hexavalent chromate film, this is because be difficult to regulate due to the thickness of trivalent chromate film.Owing to this reason, be difficult to an element self and another be made a distinction by tone, perhaps be difficult to information by the tone recognition component, as about between difference, even on the trivalent chromate film being coated to a plug hardware time, also be difficult to distinguish.
The purpose of this invention is to provide a kind of hardware that is used to have the plug of chromate film, it is substantially free of chromic chromate film and covers by a kind of, and it can distinguish by tone, and a kind of preparation method of this hardware is provided.
In order to address this problem, according to the present invention, a kind of hardware with plug of chromate film is provided, it is that plug is used hardware as spark plug or glow plug (glow plug), wherein: this hardware is coated with on its part surface at least and a kind ofly contains 95% or higher-quality chromic chromate film, with respect to the total chrome content meter; And this chromate film contains dye granule.
In composition of the present invention, with respect to the total chrome content meter, contain 95% or higher-quality chromic chromate film be formed on the plug hardware at least a portion surface on.That is to say, compare with the conventional colored chromate film that contains about 25%～35% weight of Cr VI (% quality) with respect to the total chrome content meter, chromate film according to the present invention contains a spot of Cr VI, for example, and with respect to total chrome content meter 5% quality or Cr VI still less.Therefore, can satisfy environment to reducing chromic requirement according to chromate film of the present invention.Preferably, this chromate film contains 98% or higher-quality trivalent chromium, with respect to the total chrome content meter.Preferred, the essentially no Cr VI component of this chromate film.Incidentally, idiom " essentially no Cr VI component " refers to when not detecting the Cr VI component when analyzing by x-ray photoelectron spectroscopy (XPS).
And because this chromate film contains the dye granule that is dispersed in wherein, even therefore only contain under a small amount of chromic situation at this chromate film, this chromate film also can show a kind of tone at chromate film under without any the condition of varied in thickness.The reason that this chromate film can show tone is that the light in particular range of wavelengths is absorbed by dye granule in the visible region.Therefore, thus when the component that changes dye granule changes light-absorbing wave-length coverage, can produce various tones.Therefore, also can make a distinction even be coated with the plug hardware of trivalent chromate film by tone and another plug hardware.And, in changing element, during the tone of each several part, can discern a left side and right information such as element.Incidentally, because the inside of chromate film is impregnated with dye granule, therefore do not have owing to the friction with another element causes filling in the defective that the tone of hardware shoals.
Preferably, the present invention can be used for the thickness of chromate film under the situation of 0.2 μ m～0.5 μ m.Particularly, be used for the plug of internal-combustion engine ignition,, need high corrosion-resistant as spark plug or glow plug because will high temperature or with environment that acidic components contact under use.In order to improve corrosion resistance, the inventor has successfully formed the hard chromium hydrochlorate film with this thickness on the plug hardware.But the formation of this kind hard chromium hydrochlorate film brings a kind of structure, and wherein this film almost can not contain other component such as dye granule, and this is that the structure of film becomes fine and close because the corrosion resistance of this film is improved.Yet in the present invention, dye granule is included in the trivalent chromate film that forms on the hardware that has compact texture and use in the plug that needs high corrosion-resistant especially such as spark plug or glow plug.Consequently, also can show a kind of tone even have good corrosion proof trivalent chromate film.Therefore, the range of application of trivalent chromate film can be widened, so the present invention has big industrial effect.Incidentally, if this chromate film is thinner than 0.2 μ m, then can not keep sufficient corrosion resistance and thermal endurance.And, also have a defective to be, reduce in the space of flooding in dyestuff, thereby can not show sufficient tone.If thickness is greater than 0.5 μ m, then this film tends to cracking (for example, when this element and other element are fitted together), and perhaps this film tends to come off, thereby makes corrosion resistance impaired.Preferably, with the thickness setting of chromate film in the scope of 0.3 μ m～0.5 μ m.In this thickness range, even under environment for use, particularly plug that tends to raise for temperature and because waste gas component (CO
2, NO
x) and be subject to the plug of acid attack, also can fully keep the durability of plug member.
The dye granule that is included in the chromate film can contain a kind of polar molecule compound.The trivalent chromate film is very fine and close, so the corrosion resistance excellent of this film.But according to the inventor's test, the compactness of finding film has become the obstacle that dye granule enters film inside.On the other hand, known trivalent chromate film contains polar water with the form of the hydrate of trivalent chromate.The inventor notices this point, and the dye granule of having found to contain the polar molecule compound can easily penetrate into the inside of film, this be because based in the film due to the molecular separating force of moisture dipole-dipole interaction acts on the dye granule.Because dye granule can easily penetrate in the chromate film, dye granule can form in the inside of film, even therefore be fine and close and have under the situation of good corrosion proof trivalent chromate film that at film this film also can show a kind of tone fully.Dyestuff also can further contain a kind of compound chemical substance of ion (or contain), and wherein cheland is collaborative is combined in around each metal ion.By using this kind compound, can show a kind of tone different as color center with metal ion.
Chromate technology is a kind of chemical technology of replacing and accumulate the chromium component in oxidation and wash-out underlying metal.Therefore, apply in the nothing electricity chromate technology of electric energy in the nothing external world, underlying metal must be a kind of metal that can be eluted in the chromic acid salt bath.Can on the surface of the plug hardware that constitutes by iron such as carbon steel, form a kind of with the Zn-based plating layer of zinc, so that anticorrosion as the major metal component.Thus, Zn-based plating layer is suitable for as the underlying metal that forms chromate film.Incidentally, Zn-based plating layer can form by known zinc galvanoplastic or known solution galvannealing.On the other hand, when adopting the electrolytic chromate method, chromate film in addition can bottom for nickel as the situation of the nickel coating of major metal component under or form under at bottom with the situation of iron as the iron plating of major metal component.
The first method that contains the plug hardware of chromate film produced according to the present invention has following step, to fill in hardware is immersed in a kind of mixing bath, this mixing is bathed by organic dyestuff and/or organic metal compound dyestuff are joined in the chromic acid salt bath and is made, this chromic acid salt bath is the mixture that chromic salt and trivalent chromium are used compounding ingredient, and it contains 95% or higher-quality trivalent chromium, based on the total chrome content meter.In this combination, dye granule can be included in the chromate film when forming chromate film.
Second method according to the present invention has following step: will fill in hardware and be immersed in the chromic acid salt bath, this chromic acid salt bath is chromic salt and the trivalent chromium mixture with compounding ingredient, and it contains 95% or higher-quality trivalent chromium, based on the total chrome content meter; And will fill in hardware and be immersed in the painted bath that contains organic dyestuff and/or organic metal compound dyestuff.In this combination, dye granule can penetrate in the chromate film of chromic acid salt bath formation, and dye granule can be scattered in the chromate film thus.Incidentally, the granularity that preferably is included in the dye granule in organic dyestuff and/or the organic metal compound dyestuff is as far as possible little, and is included in the chromate film its granularity of back at dye granule and is set at and is no more than 50nm.
When chromic salt and trivalent chromium with the mixture of compounding ingredient during as the chromic acid salt bath, can form the densification that is difficult to form with common chromate process and thick trivalent chromium base chromate film.The method that forms this kind chromate film is disclosed among the DE-19638176A1 in detail.
As the example that joins the compounding ingredient in the chromic acid salt bath, can use various types of chelating agents (dicarboxylic acids, tricarboxylic acids, oxyacid, hydroxydicarboxylic acid, hydroxyl tricarboxylic acids or the like effectively; For example, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, maleic acid, phthalic acid ester, terephthalic acid (TPA), tartaric acid, citric acid, malic acid, ascorbic acid or the like).Other compounding ingredient also can use.The compounding ingredient that allows to use is described among the open DE-19638176A1 of Deutsche Bundespatent special permission.
The organic dyestuff that contains the component of a kind of element or two or more elements can be used as the organic dyestuff that mixes in bath or the painted bath, and above-mentioned element is selected from Na, Cl, H, O, C, N and S.When using this kind organic dyestuff, even organic dyestuff joined under the situation in the chromic acid salt bath dye granule is included in the chromate film, even when perhaps using organic dyestuff separately, also can form the chromate film that wherein is dispersed with dye granule as painted bath.Incidentally, azo dyes can be used as organic dyestuff.
The organic metal compound dyestuff that contains the metal component of a kind of element or two or more elements also can be used as organic dyestuff, and above-mentioned element is selected from Cr and Cu.Using organic metal compound dyestuff is effective for promoting dye granule to anchor in the trivalent chromate film.The content that is included in the metal component in every kind of organic metal compound dyestuff and the water preferably is chosen as 5～800ppm.The example of organic metal compound dyestuff is a phthalocyanine dye.
General introduction ground, one aspect of the present invention relates to a kind of plug hardware with chromate film, wherein:
This hardware has a surface, chromate film is arranged to this surface-coated of small part, is benchmark with 100% weight of total chrome content in this film, contain 3 valency chromium of at least 95% weight in the chromate film, and this chromate film contains dye granule.
Another aspect of the present invention relates to a kind of spark plug, comprising:
Central electrode;
Be located at the insulator in the central electrode outside;
Be located at the metal shell in the insulator outside; And
The grounding electrode that relative central electrode is provided with, thus between grounding electrode and central electrode, form spark-discharge gap,
With the packing ring that following state uses, promptly packing ring is fixed on the bottom part of the installation threaded portion that forms on the metal shell external peripheral surface,
Wherein, in metal shell and the packing ring at least one comprises: the plug hardware with chromate film, wherein hardware has a surface, chromate film is arranged to this surface-coated of small part, 100% weight with total chrome content in this film is benchmark, the 3 valency chromium that contain at least 95% weight in the chromate film, and this chromate film contains dye granule.
Another aspect of the present invention relates to a kind of glow plug, comprises
Metal shell;
Be arranged on the resistance heater in the metal shell, thereby the fore-end that makes resistance heater stretches out from an end face of metal shell; And
The water conservancy diversion terminal is powered to resistance heater by it, and it links to each other with another end face of metal shell, thereby is exposed;
Wherein, in metal shell and the water conservancy diversion terminal at least one comprises: the plug hardware with chromate film, wherein hardware has a surface, chromate film is arranged to this surface-coated of small part, 100% weight with total chrome content in this film is benchmark, the 3 valency chromium that contain at least 95% weight in the chromate film, and this chromate film contains dye granule.
Another aspect of the present invention relates to a kind of method that is used to prepare the plug hardware with chromate film that spark plug or glow plug use, and this method comprises the steps:
With at least a the joining in the chromic acid salt bath in organic dyestuff and the organic metal compound dyestuff, this chromic acid salt bath is the mixture that chromic salt and trivalent chromium are used compounding ingredient, and 100% weight meter based on the total chrome content in the chromic acid salt bath, it contains the trivalent chromium of at least 95 weight %, and preparation mixes bath thus; And
To fill in hardware is immersed in the mixing bath.
Another aspect of the present invention relates to a kind of method that is used to prepare the plug hardware with chromate film that spark plug or glow plug use, and this method comprises the steps:
To fill in hardware and be immersed in the chromic acid salt bath, this chromic acid salt bath is chromic salt and the trivalent chromium mixture with compounding ingredient, and based on 100% weight meter of the total chrome content in the chromic acid salt bath, it contains the trivalent chromium of at least 95 weight %; And
The plug hardware is immersed at least a painted bath that contains in organic dyestuff and the organic metal compound dyestuff.
Description of drawings
[Fig. 1]
Fig. 1 is an example that has the metal element for plug use of chromate film according to the present invention.
[Fig. 2]
The schematic diagram shows of Fig. 2 be included in dye granule in the part of chromate film.
[Fig. 3]
Fig. 3 is the schematic diagram of an embodiment of the method for the preparation metal element for plug use with chromate film of the present invention.
[Fig. 4]
Fig. 4 is the schematic diagram of an embodiment of method of the metal element for plug use with chromate film of the Fig. 3 of being different from produced according to the present invention.
[Fig. 5]
Fig. 5 is the schematic diagram that dye granule penetrates into the state in the chromate film.
[Fig. 6]
Fig. 6 is an embodiment who adopts the spark plug of metal element for plug use of the present invention.
[Fig. 7]
Fig. 7 is an embodiment according to the glow plug of metal element for plug use of the present invention.
[explanation of Reference numeral and symbol]
2 insulators (electrical insulator)
3 central electrodes
4 grounding electrodes
13 terminals (spark metal element for plug use)
30 packing rings (spark metal element for plug use)
21 heaters
24 metal shells (electric heating metal element for plug use)
25 water conservancy diversion terminals (electric heating metal element for plug use)
50 mix bath
51 dye granules
55,55 ' metal shell (metal element for plug use)
56 Zn-based plating layer
57 chromate films
58 chromic acid salt baths
59 painted baths
100 spark plugs
200 glow plugs
Embodiment
Embodiment of the present invention will be elaborated with reference to the accompanying drawings.Fig. 1 shows according to the present invention the metal shell 55 as the spark plug of the plug hardware example with chromate film.In this metal shell 55, form Zn-based plating layer 56 with anticorrosion.This Zn-based plating layer 56 forms by known zinc galvanoplastic.For example, the thickness range of the Zn-based plating layer 56 that so forms is set at about 3 μ m～about 9 μ m.If the thickness of Zn-based plating layer 56 is less than 3 μ m, then the anti-corrosion effect of layer 56 is little, and because the corrosion of sacrifice property causes Zn-based plating layer 56 to exhaust, undesirable is impossible fully keep corrosion resistance.If the thickness of Zn-based plating layer 56 greater than 10 μ m, is considered from keeping corrosion proof angle, then is unnecessary, and productive rate is descended owing to coating needs the too many time.Also have a problem,, coating takes place easily peel off when this element and another combination of elements or when carrying out technology such as bending.
Fig. 3 illustrates the embodiment of the method for the plug hardware with chromate film produced according to the present invention.That is to say that the metal shell 55 that contains the Zn-based plating layer with predetermined thickness 56 that forms by known zinc galvanoplastic is submerged in to mix and bathes in 50.Mix bathing 50 preferably prepares by being used for making painted organic dyestuff of chromate film 57 and/or organic metal compound dyestuff to join the chromic acid salt bath that is used to form chromate film 57.Can use chromic acid salt bath same as described above and identical dyestuff.Therefore, metal shell 55 can be covered by the chromate film 57 that contains the dye granule 51 that is dispersed in wherein, as shown in Figure 2.Incidentally, Fig. 3 is the schematic diagram of film forming step.Although Fig. 3 illustrates metal shell 55 and simply is immersed in the situation of bathing in 50 of mixing, in fact can use known barreled method (wherein a large amount of metal shell 55 to be inserted in the container of fluid permeable, and when this container rotates in mixing bath 50, handle) so that improve production capacity.
Temperature is set at 20 ℃～80 ℃ body lotion and is preferably used as to mix and bathes 50.Be lower than 20 ℃ if bathe temperature, then, cause to keep corrosion resistance and can not be fully painted because chromate film 57 can not form fully.On the other hand, be higher than 80 ℃, then, cause chromate film 57 not form fully, thereby can not fully keep corrosion resistance because water is bathed seriously evaporation 50 from mixing if bathe temperature.In addition, the 55 required times of impregnating metal housing preferably are chosen as 20～80 seconds in mixing bath 50.If dip time is less than 20 seconds, then since dip time too weak point can not form chromate film 57, causing can not be painted fully, and can not keep corrosion resistance fully.On the other hand, if dip time was longer than 80 seconds, then be affected owing to the oversize corrosion resistance of chromate film that causes of dip time.In addition, pH value scope is chosen as 1.8～2.4 bath and is preferably used as to mix and bathes 50.If the pH value is lower than 1.8, then owing to chromate film 57 too thick chromate film 57 corrosion-vulnerable that form of causing that become.On the other hand, if the pH value is higher than 2.4, then owing to chromate film 57 too thin causing that become can not paintedly fully and undesirable be also corrosion-vulnerable of chromate film 57.
Can form the dye granule 51 that is dispersed in the chromate film 57 as shown in Figure 4.That is to say that zinc-plated metal shell 55 is immersed in the chromic acid salt bath 58 so that form chromate film 57.Then, be coated with the metal shell 55 of this chromate film 57 ' be immersed in the painted bath 59.Identical as mentioned above chromic acid salt bath can be used as chromic acid salt bath 58.Painted bath 59 is made of above-mentioned organic dyestuff and/or organic metal compound dyestuff.Painted bath 59 contains a large amount of dye granule 51.Therefore, as shown in Figure 5, dye granule 51 penetrates into the inside of the chromate film 57 that has formed.Consequently, as shown in Figure 2, can form the chromate film 57 that contains the dye granule 51 that is dispersed in wherein.In such cases, after chromate film 57 forms, metal shell 55 ' preferably be immersed in the painted bath 59, and need be through any technology with hot-air or the dry chromate film 57 of similar approach.If chromate film 57 is dried, then, cause dye granule 51 to be difficult to infiltrate in the chromate film 57 because the water that is contained in the chromate film 57 evaporates.
When by on metal shell 55, forming the metal shell 55 that chromate film 57 obtains ' when being immersed in the painted bath 59, consider the corrosion resistance of chromate film 57, the temperature of chromic acid salt bath 58 preferably sets in 20 ℃～80 ℃ scope, and in chromic acid salt bath 58 the 55 required times of impregnating metal housing be preferably set to 20 seconds～80 seconds scope in.Consequently, can form the chromate film 57 of thickness in 0.2 μ m～0.5 mu m range, and the corrosion resistance of chromate film 57 can keep well.When the pH of chromic acid salt bath value further be reduced to about 1.5～about 3 the time, can obtain this effect.Therefore, this is effectively for forming the chromate thick film, because the dissolving again of the chromate film 57 that forms can suitably be suppressed, and quickens the dissolving of bottom metal layer (Zn-based plating layer 56 that mainly contains zinc in this embodiment).
Temperature is set at 20 ℃～80 ℃ bath can be preferably used as painted bath 59.Be lower than 20 ℃ if bathe temperature, then because the permeability that dye granule 51 enters in the chromate film 57 reduces, causing can not be fully painted.On the other hand, be higher than 80 ℃, then, cause the corrosion resistance of chromate film 57 to be affected unhappyly owing to the content that is difficult to control dyestuff, pH value etc. if bathe temperature.And pH value scope is set at 2～8 bath can be preferably used as painted bath 59.If the pH value of painted bath 59 is lower than 2, then the chromate film 57 of Xing Chenging is subject to the corrosion of the acid constituents in the painted bath 59.On the other hand, if the pH value is higher than 8, then chromate film 57 is subject to the corrosion of the basic component in the painted bath 59 also unhappyly.In addition, the inventor finds, when the alkaline side of the pH of painted bath 59 value deflection, and the permeability reduction of dye granule 51.
Impregnating metal housing 55 in painted bath 59 ' required time can be preferably set to 20 seconds～80 seconds scope in.If dip time is shorter than 20 seconds, then dye granule 51 can not be infiltrated, thereby can not obtain good painted owing to dip time is too short.On the other hand, if dip time was longer than 80 seconds, then the permeability of dye granule 51 is constant.Dip time is longer than 80 seconds corrosion resistances to chromate film 57 and is produced the influence of not expecting, and causes reducing productivity ratio.
Metal shell 55 is used for spark plug as shown in Figure 6.Spark plug 100 as shown in Figure 6 has a central electrode 3, an insulator 2 that is positioned at central electrode 3 outsides, a metal shell 55 that is positioned at insulator 2 outsides, and a grounding electrode 4 that is oppositely arranged with central electrode 3, between grounding electrode 4 and central electrode 3, form spark-discharge gap g thus.In addition, form through hole 6 in the inboard of insulator 2, thereby make the central electrode 3 can axially being installed in the through hole 6 along insulator 2.Terminal 13 inserts and is fixed to a side end of through hole 6, and central electrode 3 inserts and be fixed to the end side of through hole 6 simultaneously.Terminal 13 has screw-type terminal 13a, the female thread portion threaded engagement of itself and through hole 6, and end cap 13b and screw-type terminal 13 threaded engagement.In addition, terminal 13 can be the monolithic devices terminal, and wherein screw-type terminal 13a is interconnected into integral body mutually with end cap 13b.As mentioned above, metal shell 55 is plug hardwares of the present invention.The surface of plug hardware is covered by chromate film 57 of the present invention.Zn-based plating layer 56 forms as the bottom metal layer of plug hardware.Incidentally, terminal 13 can also be a plug hardware of the present invention.Notion " terminal 13 " can comprise screw-type terminal 13a, end cap 13b and monolithic devices terminal.
Metal shell 55 is by making and be configured as cylindrical shape such as the metal of carbon steel.Metal shell 55 constitutes a shell that holds spark plug 100.Be used for the plug 100 installation threaded portions 7 that are installed on the engine slide block (not shown) are formed on the outer surface of metal shell 55.Packing ring 30 is installed in the bottom part of the installation threaded portion 7 that forms on metal shell 55 outer surfaces.Packing ring 30 is endless members, by the metal sheet acquisition of bending such as carbon steel.Cylinder head side pack into when having in the hole of screw thread when threaded portion 7 will be installed, packing ring 30 between the opening perimeter marginal portion of the flange-like airtight portion 1f of metal shell 55 1 sides and screwed hole by axial compression.Consequently, packing ring 30 distortion, thus be crushed, so packing ring 30 plays the effect in the gap between sealing thread hole and the installation threaded portion 7.Incidentally, packing ring 30 also can be used as plug hardware of the present invention.That is to say that packing ring 30 also can form chromate film 57, so that anticorrosion, and manifest tone by dye granule 51.Form on any other hardware of the spark plug 100 that certain chromate film 57 according to the present invention also can not addressed hereinbefore.
Plug hardware according to the present invention can be used as the hardware that is used for glow plug, as shown in Figure 7.Glow plug 200 has a kind of structure, and wherein resistance heater 21 is installed in the metal shell 24, thereby the fore-end 21a that makes resistance heater 21 stretches out from an end face of metal shell 24.And the water conservancy diversion terminal 25 of powering to heater 21 links to each other with metal shell 24 other end sides, thereby is exposed.Plug hardware according to the present invention can be used as metal shell 24 and/or water conservancy diversion terminal 25.At least a portion surface of metal shell 24 or water conservancy diversion terminal 25 is covered by chromate film 57 according to the present invention.Zn-based plating layer 56 is formed on below the chromate film 57 as bottom metal layer.Certainly can form on any other hardware of NM hereinbefore glow plug 200 according to chromate film 57 of the present invention.In addition, glow plug can have a kind of structure, wherein be provided for water conservancy diversion end axle to heater 21 power supplies, thereby the end section that makes water conservancy diversion terminal 25 stretches out from another end face of metal shell, and wherein is used for the water conservancy diversion cable is fixed to the male thread portion threaded engagement that nut on the water conservancy diversion terminal 25 and water conservancy diversion terminal 25 end sections form.In such cases, plug hardware according to the present invention also comprises nut except that metal shell 24.Incidentally, certainly except that spark plug 100 shown in Fig. 6 and 7 and glow plug 200, the present invention can also be used to have the hardware of the plug of any other structure.
Embodiment
[embodiment 1]
As plug hardware, utilize 55 pairs of effects of the present invention of metal shell of spark plug to test with chromate film.Incidentally, although present embodiment explanation one embodiment of the invention in the case of without departing from the spirit of the present invention, can be carried out other variation to it on the basis of those skilled in the art's common practise.
The cold forging carbon steel wire SWCH8A that defines among the JIS-G 3539-1999 prepares the metal shell 55 with shape shown in Figure 1 as raw material by cold forging.Metal shell 55 being imposed the zinc that utilizes known alkaline cyanide to bathe electroplate, is the Zn-based plating layer 56 of about 6 μ m thereby form thickness.
Then, with 50g chromium chloride (III) (CrCl
36H
2O), 3g cobalt nitrate (III) (Co (NO
3)
2), 100g sodium nitrate (NaNO
3) and the 31.2g malonic acid be dissolved in 1 liter the deionized water, thereby preparation chromic acid salt bath 58.Simultaneously the liquid temperature of chromic acid salt bath remains on 60 ℃ by heater, the aqueous solution of NaOH is joined in the chromic acid salt bath, so that the pH value of chromic acid salt bath is adjusted to 2.0.Then, the metal shell 55 that is coated with zinc is immersed in the chromic acid salt bath 58 60 seconds, thereby forms trivalent chromium base chromate film 57.
The metal shell 55 that forms in this way is immersed in the painted bath 59 of organic dyestuff, based on condition listed in the table 1.Particularly, with Okuno ChemicalIndustries Co., the Top Zinc Color Process Y-5 that Ltd. produces joins in the painted bath by every liter of 4g as organic dyestuff.Top Zinc Color Process Y-5 contains the polar molecule compound.Then, observe by eyes, the tone surperficial to the tone on spark plug metal shell 55 ' surface and spark plug metal shell 55 ' (sample 11) that only dipping obtains in the chromic acid salt bath as a comparative example compares mutually.Do not observe be evaluated as " * " of tone difference.But confirmation has be evaluated as " △ " of tone difference tone light.Be evaluated as " zero " with enough tones.Incidentally, the tone on spark plug metal shell 55 ' surface is essentially yellow.
" 5.Neutral Salt Water Spray Test Method " in the corrosion resistance of coating method of testing that will in JIS-H8502-1988, define on the other hand, be used for each metal shell 55 '.After this test is carried out 96 hours, observe the degree that detects Zn-based plating layer 56 corrosion gained white rust stainings with eyes.Evaluation criteria is set as follows.
Zero (excellence): the ratio that white rust staining accounts for whole surface area is lower than 10%.
△ (well): the ratio that white rust staining accounts for whole surface area is not less than 10% and be lower than 20%.
* (poor): the ratio that white rust staining accounts for whole surface area is higher than 20%.
In addition, the thickness of chromate film 57 carries out actual measurement with SEM based on the part of each test sample.Incidentally, for the ease of observing chromate film 57, on the surface of chromate film 57, form the Au film by sputtering method.Because the rete of the chromate film 57 that conductivity is low is dark, therefore in the SEM image, confirm the image of chromate film easily based on contrast in the SEM image.
Table 1 shows assessment result.
[table 1]
| Test piece number (Test pc No.) | The bath temperature (℃) | Body lotion pH value | Dip time (second) | Apparent | Corrosion resistance | |
| 1 | 10 | 6 | 60 | △ | ○ | |
| 2 | 20 | ○ | ○ | |||
| 3 | 40 | ○ | ○ | |||
| 4 | 80 | ○ | ○ | |||
| 5 | 90 | ○ | △ | |||
| 6 | 60 | 1 | ○ | × | ||
| 7 | 2 | ○ | ○ | |||
| 8 | 4 | ○ | ○ | |||
| 9 | 7 | ○ | ○ | |||
| 10 | 8 | ○ | ○ | |||
| 11 | 9 | △ | △ | |||
| 12 | 6 | 10 | △ | ○ | ||
| 13 | 20 | ○ | ○ | |||
| 14 | 80 | ○ | ○ | |||
| 15 | 120 | ○ | △ | |||
| 16 | Not painted | × | ○ | |||
From table 1 obviously as seen, trivalent chromate film 57 can be painted by preparation method of the present invention.Also obviously as seen, the ph value of, body lotion warm when bathing and dip time are chosen as and are not less than 20 ℃, are not higher than 8 and when being not less than 20 seconds respectively, can obtain good painted.On the other hand, also obviously as seen, be higher than 80 ℃, the pH value of body lotion and be not higher than 1 or dip time when being longer than 90 seconds, the corrosion resistance reduction of film when bathing temperature.
[embodiment 2]
The metal shell 55 of spark plug is according to the method preparation identical with embodiment 1.Spark plug metal shell 55 is imposed the zinc galvanoplastic of utilizing alkaline hydride to bathe, is the Zn-based plating layer 56 of 6 μ m thereby form thickness.
Then, chromic acid salt bath 58 is prepared as follows, with 50g chromium chloride (III) (CrCl
36H
2O), 3g cobalt nitrate (II) (Co (NO
3)
2), 100g sodium nitrate (NaNO
3), 31.2g malonic acid and 4g organic dyestuff (TOP ZINC COLORPROCESS Y-5) be dissolved in 1 liter the deionized water.Incidentally, the aqueous solution by adding NaOH is adjusted to 2.0 with the pH value of body lotion.
Spark plug metal shell 55 is immersed in the mixing of regulating as stated above bathes in 50, based on the condition shown in the table 2.Then, observe, the surperficial tone of impregnated spark plug metal shell 55 (sample 7) in the tone on spark plug metal shell 55 ' surface and the only chromic acid salt bath in embodiment 1 is as a comparative example compared by eyes.To not observe be evaluated as " * " of tone difference.But confirmation has be evaluated as " △ " of tone difference tone light.Be evaluated as " zero " with enough tones.Incidentally, the tone on spark plug metal shell 55 ' surface is essentially yellow.
On the other hand, " the 5.Neutral Salt Water Spray Test Method " in the corrosion resistance of coating method of testing that will in JIS-H8502-1988, define, according to the method identical with embodiment 1, be used for the metal shell 55 of each spark plug '.After this test is carried out 96 hours, observe the degree that detects Zn-based plating layer 56 corrosion gained white rust stainings with eyes.Evaluation criteria is set as follows.
Zero (excellence): the ratio that white rust staining accounts for whole surface area is lower than 10%.
△ (well): the ratio that white rust staining accounts for whole surface area is not less than 10% and be lower than 20%.
* (poor): the ratio that white rust staining accounts for whole surface area is higher than 20%.
In addition, the thickness of chromate film 57 carries out actual measurement with SEM based on the part of each test sample.Incidentally, for the ease of observing chromate film 57, on the surface of chromate film 57, form the Au film by sputtering method.Because the rete of the chromate film 57 that conductivity is low is dark, therefore in the SEM image, confirm the image of chromate film easily based on contrast in the SEM image.
Table 2 shows assessment result.
[table 2]
| Test piece number (Test pc No.) | PH | The bath temperature (℃) | Dip time (second) | Apparent tone | Corrosion resistance | Chromate thickness (μ m) |
| 1 | 1.6 | 60 | 60 | ○ | △ | 0.51 |
| 2 | 1.8 | ○ | ○ | 0.50 | ||
| 3 | 2.4 | ○ | ○ | 0.20 | ||
| 4 | 2.8 | △ | △ | 0.18 | ||
| 5 | 2.0 | 10 | △ | △ | 0.18 | |
| 6 | 20 | ○ | ○ | 0.21 | ||
| 7 | 40 | ○ | ○ | 0.32 | ||
| 8 | 60 | ○ | ○ | 0.41 | ||
| 9 | 80 | ○ | ○ | 0.50 | ||
| 10 | 90 | ○ | △ | 0.57 | ||
| 11 | 60 | 10 | △ | △ | 0.19 | |
| 12 | 20 | ○ | ○ | 0.21 | ||
| 13 | 80 | ○ | ○ | 0.50 | ||
| 14 | 120 | ○ | △ | 0.61 | ||
| 15 | Not painted | × | ○ | 0.42 | ||
From table 2 obviously as seen, trivalent chromate film 57 can be painted by preparation method of the present invention.Also obviously as seen, when bathing that temperature is lower than that 20 ℃, dip time are shorter than 20 seconds or pH when being higher than 2.4, the trivalent chromate film becomes and is thinner than 0.2 μ m, so corrosion resistance reduction and can not be fully painted.Also obviously as seen, when the bath temperature is higher than 80 ℃, dip time was longer than 80 seconds or pH when being lower than 1.8, the trivalent chromate film becomes and is thicker than 0.5 μ m, thereby has reduced corrosion resistance.Therefore, when bathe that temperature, dip time and pH are chosen as 20 ℃～80 ℃, 20 seconds～80 seconds respectively and 1.8～2.4 scope in the time, can obtain good painted and can form trivalent chromate film with good corrosion resistance.
Incidentally, the existence of chromium detects by x-ray photoelectron spectroscopy (XPS) in the chromate film 57 of each sample.Consequently, confirm that chromate film 57 contains the trivalent chromium that accounts for total chrome content 100 weight %, that is to say, do not detect Cr VI.Incidentally, carry out with ESCALAB 220iXL instrument (VGScientific) by the analysis of x-ray photoelectron spectroscopy.
As creative product of the present invention, each sample 2,5,6 of embodiment 1 and 9 and each sample 2 and 3 of embodiment 2 in, the tone of chromate film 57 is measured in order to the laboratory colour system of numeral.Consequently, confirm that the brightness L of the tone of chromate film is 60～90, tone a is-40～40, and tone b is 0～60, and chromaticity C is 10～60.Incidentally, with laboratory colour system measurement is by using by MinoltaCo., Ltd. the spectrophotometer CM-3500d of Sheng Chaning, carry out under the following conditions: light source: 2 ° of D65, reference colour system: spectral reflectance, conventional reverberation is handled: SCI, measure diameter: Φ 8mm, target shield: Φ 3mm.
The application is based on Japanese patent application JP2002-265796, the applying date is on September 11st, 2002, and Japanese patent application JP 2001-347451, and the applying date is November 13 calendar year 2001, the full content of above-mentioned patent application is incorporated herein by reference, and its content as previously mentioned.
Claims (8)
1, a kind of plug hardware with chromate film, wherein:
This hardware has a surface, chromate film is arranged to this surface-coated of small part, is benchmark with 100% weight of total chrome content in this film, contain 3 valency chromium of at least 95% weight in the chromate film, and this chromate film contains dye granule.
2, according to the plug hardware with chromate film of claim 1, wherein dye granule contains a kind of polar molecule compound.
3, according to the plug hardware with chromate film of claim 1, wherein the thickness of chromate film is 0.2 μ m～0.5 μ m.
4, a kind of spark plug comprises:
Central electrode;
Be located at the insulator in the central electrode outside;
Be located at the metal shell in the insulator outside; And
The grounding electrode that relative central electrode is provided with, thus between grounding electrode and central electrode, form spark-discharge gap,
With the packing ring that following state uses, promptly packing ring is fixed on the bottom part of the installation threaded portion that forms on the metal shell external peripheral surface,
Wherein, in metal shell and the packing ring at least one comprises: the plug hardware with chromate film, wherein hardware has a surface, chromate film is arranged to this surface-coated of small part, 100% weight with total chrome content in this film is benchmark, the 3 valency chromium that contain at least 95% weight in the chromate film, and this chromate film contains dye granule.
5, a kind of glow plug comprises
Metal shell;
Be arranged on the resistance heater in the metal shell, thereby the fore-end that makes resistance heater stretches out from an end face of metal shell; And
The water conservancy diversion terminal is powered to resistance heater by it, and it links to each other with another end face of metal shell, thereby is exposed;
Wherein, in metal shell and the water conservancy diversion terminal at least one comprises: the plug hardware with chromate film, wherein hardware has a surface, chromate film is arranged to this surface-coated of small part, 100% weight with total chrome content in this film is benchmark, the 3 valency chromium that contain at least 95% weight in the chromate film, and this chromate film contains dye granule.
6, a kind of method that is used to prepare the plug hardware with chromate film that spark plug or glow plug use, this method comprises the steps:
With at least a the joining in the chromic acid salt bath in organic dyestuff and the organic metal compound dyestuff, this chromic acid salt bath is the mixture that chromic salt and trivalent chromium are used compounding ingredient, and 100% weight meter based on the total chrome content in the chromic acid salt bath, it contains the trivalent chromium of at least 95 weight %, and preparation mixes bath thus; And
To fill in hardware is immersed in the mixing bath.
7, a kind of method that is used to prepare the plug hardware with chromate film that spark plug or glow plug use, this method comprises the steps:
To fill in hardware and be immersed in the chromic acid salt bath, this chromic acid salt bath is chromic salt and the trivalent chromium mixture with compounding ingredient, and based on 100% weight meter of the total chrome content in the chromic acid salt bath, it contains the trivalent chromium of at least 95 weight %; And
The plug hardware is immersed at least a painted bath that contains in organic dyestuff and the organic metal compound dyestuff.
8, according to the method for claim 7, wherein the temperature of painted bath is 20 ℃-80 ℃, and the pH value is 2-8, and the dipping in painted bath carried out 20 seconds-80 seconds.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP347451/2001 | 2001-11-13 | ||
| JP2001347451 | 2001-11-13 | ||
| JP2002265796A JP4121342B2 (en) | 2001-11-13 | 2002-09-11 | Metal part for plug with chromate coating and method for manufacturing the same |
| JP265796/2002 | 2002-09-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1419323A CN1419323A (en) | 2003-05-21 |
| CN100344037C true CN100344037C (en) | 2007-10-17 |
Family
ID=26624497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021504563A Expired - Lifetime CN100344037C (en) | 2001-11-13 | 2002-11-13 | Metal element with chromate membrane for plug use and preparation process thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6838809B2 (en) |
| EP (2) | EP1473810B1 (en) |
| JP (1) | JP4121342B2 (en) |
| CN (1) | CN100344037C (en) |
| DE (2) | DE60235120D1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10305449A1 (en) * | 2003-02-11 | 2004-08-26 | Walter Hillebrand Gmbh & Co. | Reaction solution for producing colored passivation film on zinc and its alloys, e.g. on iron or steel, is based on aqueous acid solution containing trivalent chromium ions and contains quinoline dye, preferably quinoline yellow |
| JP4446233B2 (en) * | 2004-03-03 | 2010-04-07 | ディップソール株式会社 | Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof |
| KR100627380B1 (en) * | 2006-02-02 | 2006-09-25 | 기양금속공업(주) | Aluminium material of chemical coating method that use the trivalent chromate |
| US20080050608A1 (en) * | 2006-08-25 | 2008-02-28 | Mcfaul Surry D | Metal coating process and product |
| JP4260838B2 (en) * | 2006-12-28 | 2009-04-30 | 日本リークレス工業株式会社 | Metal gasket material plate and manufacturing method thereof |
| DE102007044967A1 (en) * | 2007-09-19 | 2009-04-02 | Beru Ag | Glow plug with coking-optimized design, special annular gap formation |
| JP4805400B1 (en) * | 2010-08-11 | 2011-11-02 | 日本特殊陶業株式会社 | Spark plug and metal shell for spark plug |
| JP6314133B2 (en) * | 2012-06-08 | 2018-04-18 | ピーアールシー−デソト インターナショナル，インコーポレイティド | Indicator paint for metal surface |
| KR20140142934A (en) * | 2013-06-05 | 2014-12-15 | 우진공업주식회사 | Metal shell of glow flug for diesel engine and method for fabricating the same |
| EP3577172B1 (en) * | 2017-02-01 | 2022-08-24 | Chemeon Surface Technology, LLC | Dyed trivalent chromium conversion coatings and methods of using same |
| JP7276976B1 (en) | 2022-02-28 | 2023-05-18 | Ｎｅｃプラットフォームズ株式会社 | Conveying device and method |
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| US4967116A (en) * | 1987-12-10 | 1990-10-30 | Ngk Spark Plug Co. Ltd. | Spark plug having heat- and corrosion-resistant surface |
| CN1059293C (en) * | 1996-06-28 | 2000-12-06 | 日本特殊陶业株式会社 | Spark plug |
| US6236148B1 (en) * | 1999-02-25 | 2001-05-22 | Ngk Spark Plug Co., Ltd. | Spark plug with specific metal shell coating |
| EP1128508A2 (en) * | 2000-02-24 | 2001-08-29 | Ngk Spark Plug Co., Ltd | Metal member with chromate coat, spark plug with chromate coat and manufacturing methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3392008B2 (en) | 1996-10-30 | 2003-03-31 | 日本表面化学株式会社 | Metal protective film forming treatment agent and treatment method |
| ZA812807B (en) | 1980-05-30 | 1982-04-28 | Champion Spark Plug Co | Preventing corrosion of zinc and cadmium |
| JPS61587A (en) | 1984-06-12 | 1986-01-06 | C Uyemura & Co Ltd | Solution for chemical conversion treatment |
| JP3333611B2 (en) | 1993-11-09 | 2002-10-15 | 日本パーカライジング株式会社 | Hexavalent chromium-free chemical conversion surface treatment agent for aluminum and aluminum alloys |
| DE19615664A1 (en) | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chromium (VI) free chromate layer and process for its production |
| DE19638176A1 (en) | 1996-09-18 | 1998-04-16 | Surtec Produkte Und Systeme Fu | Corrosion resistant hexavalent chromium-free chromate coating |
| JP2000048980A (en) | 1998-07-24 | 2000-02-18 | Toshiba Lighting & Technology Corp | Discharge lamp lighting device and lighting system |
| JP4529208B2 (en) | 1998-12-09 | 2010-08-25 | ユケン工業株式会社 | Hexavalent chromium-free chemical conversion treatment liquid and method for producing a zinc-based plating material provided with a chemical conversion treatment film formed by the chemical conversion treatment liquid |
| JP2000249340A (en) * | 1999-02-25 | 2000-09-12 | Ngk Spark Plug Co Ltd | Glow plug and manufacture thereof |
| JP3344960B2 (en) * | 1999-02-25 | 2002-11-18 | 日本特殊陶業株式会社 | Spark plug and its manufacturing method |
-
2002
- 2002-09-11 JP JP2002265796A patent/JP4121342B2/en not_active Expired - Fee Related
- 2002-11-13 EP EP04017761A patent/EP1473810B1/en not_active Expired - Lifetime
- 2002-11-13 US US10/292,455 patent/US6838809B2/en not_active Expired - Fee Related
- 2002-11-13 DE DE60235120T patent/DE60235120D1/en not_active Expired - Lifetime
- 2002-11-13 EP EP02025535A patent/EP1313188B1/en not_active Expired - Lifetime
- 2002-11-13 CN CNB021504563A patent/CN100344037C/en not_active Expired - Lifetime
- 2002-11-13 DE DE60204102T patent/DE60204102T2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4967116A (en) * | 1987-12-10 | 1990-10-30 | Ngk Spark Plug Co. Ltd. | Spark plug having heat- and corrosion-resistant surface |
| CN1059293C (en) * | 1996-06-28 | 2000-12-06 | 日本特殊陶业株式会社 | Spark plug |
| US6236148B1 (en) * | 1999-02-25 | 2001-05-22 | Ngk Spark Plug Co., Ltd. | Spark plug with specific metal shell coating |
| EP1128508A2 (en) * | 2000-02-24 | 2001-08-29 | Ngk Spark Plug Co., Ltd | Metal member with chromate coat, spark plug with chromate coat and manufacturing methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030214208A1 (en) | 2003-11-20 |
| EP1473810B1 (en) | 2010-01-13 |
| DE60204102D1 (en) | 2005-06-16 |
| EP1313188B1 (en) | 2005-05-11 |
| DE60235120D1 (en) | 2010-03-04 |
| JP4121342B2 (en) | 2008-07-23 |
| JP2003217791A (en) | 2003-07-31 |
| EP1473810A2 (en) | 2004-11-03 |
| EP1313188A2 (en) | 2003-05-21 |
| EP1313188A3 (en) | 2003-10-01 |
| DE60204102T2 (en) | 2005-11-17 |
| CN1419323A (en) | 2003-05-21 |
| EP1473810A3 (en) | 2008-10-29 |
| US6838809B2 (en) | 2005-01-04 |
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